WO2000020479A1

WO2000020479A1 - Amino-functional urea-alkoxy-silanes, a method for the production thereof and their use

Info

Publication number: WO2000020479A1
Application number: PCT/EP1999/007114
Authority: WO
Inventors: Raymond Audenaert; Joachim Simon; Detlev Joachimi; Alexander Karbach
Original assignee: Bayer Aktiengesellschaft; Bayer Antwerpen N.V.
Priority date: 1998-10-07
Filing date: 1999-09-24
Publication date: 2000-04-13
Also published as: DE19846099C2; US6320066B1; AU6196099A; EP1117717B1; TR200100955T2; ATE228537T1; DE59903587D1; EP1117717A1; DE19846099A1; JP2002526615A; ES2188250T3

Abstract

The invention relates to water-soluble, oligomeric and polymeric alkoxy-silane compounds which comprise both urea groups as well as amino groups. The invention also relates to a method for producing said compounds and to their use for modifying surfaces of solids, especially for promoting adhesion to glass surfaces and for finishing glass fibers.

Description

Amino functional urea alkoxy silanes, a process for their preparation and their use

The present invention relates to water-soluble, oligomeric and polymeric alkoxysilane compounds which have both urea groups and amino groups, a process for their preparation and their use for surface modification of solids, in particular for promoting adhesion to glass surfaces and for sizing glass fibers.

The use of functional mono-, bis- and tris-alkoxysilanes for promoting adhesion and modification of hydroxy-functional surfaces, especially glass surfaces, is known (Kirk-Othmer, Enzyclopedia of Chemical Technology, Vol. 20, 3rd Ed., J. Wiley, NY) . The general idea is that adhesion is created by hydrolysis of the alkoxysilane groups to silanol groups and by condensation with hydroxyl groups on the surface (E. Pluedemann, Silane Coupling Agents, Plenum Press, N.Y. 1982).

Alkoxysilanes which have an additional functional group which is capable of further specific or non-specific ones are preferably used

To make bonds. For example, alkoxysilanes with methacrylic, acrylic, vinyl, amino or urea groups are used. Functional alkoxysilanes which are able to react e.g. via the reaction of the amino group e.g. enter into further covalent bonds with epoxides, carboxylic acids, isocyanates, carboxylic anhydrides etc. These covalent bonds in particular bear

Dimensions for imparting adhesion and coupling to glass surfaces. Examples of these are in particular amino-alkoxysilanes and aminoalkyl-amino-alkoxysilanes (US Pat. No. 2,971,864, US Pat. No. 3,234,159).

Aminosilanes, for example 3-aminopropyltrialkoxysilane and N-aminoefhyl-3-aminopropyl trialkoxysilane are commercial products, for example from Huls AG, Mari. The ability to impart adhesion is evidently particularly good when oligomeric or polymeric alkoxysilanes are used which have more than one alkoxysilane group per molecule and additionally additional reactive functional groups. Examples include amino-amido-functional polymers or oligomers with pendant alkoxysilane groups (US 3,445,441, US 3,746,738, US 4,1263,073) or polyesters with side alkoxysilane groups (EP 43 109). These materials are shown to be advantageous for application from aqueous solutions in US Pat. No. 4,244,844. However, these products have undesirable yellow to brown colorations for technical applications.

US 4 163 073 and EP 43 109 describe polyesters with amino groups and alkoxysilane groups which are attached to the main chain of unsaturated polyesters.

It is also known that alkoxysilanes containing urea groups are advantageous for promoting adhesion to glass surfaces (Progr. Colloid Polym. Sei. 1997, 105: 80-84).

FR 2 678 936 describes polyurea-polyurethane-macromers with alkoxysilane

End groups described. These compounds contain more than one alkoxysilane group per molecule and no free amino groups.

US Pat. No. 4,374,237 discloses polyurethane prepolymers with bisfunctional alkoxysilane end groups. These connections contain terminal

Alkoxysilane groups, as well as urea groups and no free amino groups.

3-ureidopropyl trialkoxysilanes are e.g. Commercial products from Hüls AG, Mari. The

Preparation and use of ureido silanes is described in US 4,626,560, US 3,754,971 and US 4,046,794 and their use in WO 94/13473.

With regard to the alkoxysilane groups, these silanes are monofunctional ionic compounds considerations and have an alkoxysilane group with a maximum of three hydrolyzable alkoxy groups or three hydroxyl groups per molecule. Such silanes have poorer properties than those adhesion promoters which have more than one alkoxysilane group per molecule.

In US 3,493,461, ureido silanes are prepared from mono-isocyanate-functional alkoxysilanes by reaction with amines. According to EP 406 160, urea-alkoxysilane compounds are produced from mono-, bis-, tris- and higher-functional isocyanates with aminoalkoxysilanes. From WO 94/09013 UV-curable or polymerizable oligomers with terminal urea groups pass through

Alkoxysilane groups are functionalized. The adhesive strength of these compounds is very limited due to the lack of free amino groups.

For the purpose of promoting adhesion, oligomeric and polymeric alkoxysilane compounds which can be applied from water have proven to be advantageous.

At the same time, the water activates the alkoxysilane compounds by initiating hydrolysis to the reactive silanol groups.

The derivatives which are water-soluble or can be applied from the aqueous phase are therefore of particular importance in the case of aminoalkoxysilanes. These derivatives play a special role in the coating of glass fibers or in the formulation of water-based adhesion promoters.

Alkoxysilane compounds with urea groups which have been developed for the purpose of miscibility with moisture-curing PU systems and whose amino groups have been reacted further by imino or aminal groups, so that no reactive amino groups are present, are described in EP 406 106. The mediation of these connections is limited. It was therefore an object to provide and produce suitable, colorless, oligomeric or polymeric adhesion promoters for oxidic surfaces which can be applied from aqueous solvents.

Surprisingly, it has been found that the reaction of diaminoalkoxysilanes, e.g. N-aminoethyl-3-aminopropyltrialkoxysilane, with diisocyanates leads to uncrosslinked, soluble, linear urea oligomers and polymers with free terminal amino groups and lateral alkoxysilane groups, which are stable in storage in organic solution and which give stable solutions in aqueous solvents. In particular, the combination of free amino groups, urea groups and more than one alkoxysilane group per molecule leads to outstanding properties.

The invention relates to water-soluble, oligomeric or polymeric amino-functional urea-alkoxy-silane compounds obtainable by reaction of

a) 1 to 1.8 equivalents of a diisocyanate

b) 2 equivalents of a diamine consisting of

bl) 80 to 100% by weight of a diaminoalkoxysilane of the formula (I)

HN (Rl) -ZN (H) -Y-Si (OR2) ₍₃ _ _a) R3 _a (I)

in which

Z = C _] -C ₆ alkylene, C ₅ -C _{j 0} cycloalkylene or arylene,

R ¹ - H, C, -C ₆ alkyl or C ₅ -C ₁₀ cycloalkyl,

Y = C ₃ -C ₆ alkylene, R ² = C, -C ₆ alkyl or C ₅ -C _{j 0} cycloalkyl,

a = 0 to 2 and

R ³ = C _r C ₆ alkyl or C ₅ -C _{] 0} cycloalkyl, and

b2) 0 to 20% by weight of at least one nonionic, hydrophilic compound containing ether groups which has two groups which are reactive toward isocyanate groups, in particular hydroxyl and / or amino groups, per molecule.

Aromatic, aliphatic, heterocyclic, monocyclic and polycyclic, bifunctional isocyanate compounds are preferred as diisocyanates.

Diisocyanates of the formula (II)

OCN-R-NCO (II)

in which

R = C _r C ₆ alkylene, C ₅ -C ₁₅ cycloalkylene, C ₆ -C ₁₄ arylene, C ₇ -C ₂₀ arylalkylene or C ₇ -C ₂ o-alkylarylene

means.

Diisocyanates of the type ethylene diisocyanate, 1,2 diisocyanatopropane, 1,3 diisocyanatopropane, 1,4 butylene diisocyanate (BDI), 1,6 diisocyanatohexane (HDI), 1,2 diisocyanatocyclohexane, 1,3 diisocyanatocyclohexane, 1 , 4 diisocyanatobenzene, bis (4-isocyanatocyclohexyl) methane (H12MDI), bis (4-isocyanatocyclohexenyl) meιhan, bis (4-isocyanatophenyl) methane (MDI), 2,4 and 2,6 toluenediisocyanate (TDI), 1, 5 diiso- cyanatonaphthalene, hydrogenated toluene diisocyanate, l-isocyanatomefethyl-5-isocyanato-l, 3,3, trimethyl-cyclohexane (isophorone diisocyanate, IPDI), 1,6-diisocyanato-2,2,4-trimethylhexane are preferred.

1,6-Diisocyanatohexane and 1-isocyanatomethyl-5-isocyanate-1,3,3-trimethylcyclohexane (isophorone diisocyanate) are particularly preferred.

Furthermore, bis-functional isocyanates which have been prepared by reacting or oligomerizing diisocyanates can preferably be used on average. For example, preferably, allophanate, uretdione or biuret group-containing products (such as Desmodur® N 100 from Bayer AG, Leverkusen) or partially trimerized polyisocyanates containing iminooxadiazinedione or iso- cyanurate-rings have (such as Desmodur ^® N 3400 Bayer AG) can be used.

Particularly suitable diaminoalkoxysilanes are N-ß- (aminoethyl) -γ-aminopropyltrimethoxysilane (Dynasilan® Damo from Hüls AG), N-ß- (aminoethyl) -γ-aminopropyltriethoxysilane, N-ß- (aminoethyl) -γ- aminopropylmethyldimethoxysilane, N-ß- (aminoethyl) -N-ß- (aminoethyl) -γ-aminopropyltrimethoxysilane:

(CH3-CH ₂ -O) ₃ Si-CH2-CH ₂ -CH ₂ -NH-CH ₂ -CH ₂ -NH ₂ (CH ₃ O) ₃ Si-CH ₂ CH ₂ CH ₂ -NH-CH ₂ CH2- NH ₂

(C ₂ H ₅ O) ₂ (CH ₃ ) Si-CH ₂ CH ₂ CH ₂ - (NH-CH ₂ CH ₂ ) ₃ -NHCH ₂ CH ₂ CH ₂ - Si (CH ₃ ) (OC ₂ H ₅ ) ₂ (CH ₃ O) ₃ Si-CH ₂ CH ₂ CH ₂ -NH-CH ₂ -C ₆ H ₄ -NH-H ₂ CH ₂ -Si (OCH ₃ ) ₃

(CH ₃ O) ₂ (CH ₃ ) -Si-CH ₂ CH ₂ CH ₂ -NH-CH ₂ CH ₂ -NH-CH ₂ CH ₂ CH ₂ -Si (CH ₃ ) (OCH ₃ ) ₂

N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane is particularly preferred.

Compounds of the following formula are particularly suitable as compounds under b2): NH ₂ - (XO-) _a -V-NH ₂

in which

XC _j -Cg alkylene, branched or unbranched, a I to 100 and

V Ci-Cg-alkylene, branched or unbranched, mean.

The polyether chains of these compounds preferably consist of at least 80

% By weight, particularly preferably 100% by weight, of ethylene oxide units, it being possible for propylene oxide units to be present in addition to these. Preferred nonionic, hydrophilic compounds are, for example, polyethylene glycols with molecular weights of 300 to 6,000 (e.g. Carbowax®300, 400, 1,000, 1,500, 2,000, 6,000 from Union Carbide), difunctional ether diamines, such as e.g. 4,7-dioxadecane-l, 10-diamine,

4,9-dioxadodecane-l, 12-diamine, 4,7,10-trioxadecane-l, 13-diamine, bis- (3-aminopropyl) -polytetrahydrofuran, bis- (3-aminopropyl) -polytetrahydrofuran, bis- (3-aminopropyl) polytetrahydrofuran (products Carbowax ^® 750, 1100, 2100 from BASF), and polyether amines (such as Jeffamine ^® D 230, D 400, D 2000, XTJ 510 (D 4000), ED 600, ED 900 , ED 2 003, ED 4 000, EDR 148 (XTJ 504) from Texaco

Chemical Company).

The following difunctional ether diamines are very particularly preferred: 4,7-dioxadecan-1, 10-diamine; 4,9-dioxadodecane-1, 12-diamine; 4,7,10-trioxadecane-1,13-diamine; Bis- (3-aminopropyl) polytetrahydrofuran 750, bis- (3-aminopropyl) -polytetra- hydrofuran 1100, bis (3-aminopropyl) polytetrahydrofuran 2100 from BASF and Jeffamine ^® D 230, D 400, D 2000 , XTJ 510 (D 4,000), ED 600, ED 900, ED 2 003, ED 4 000, EDR 148 (XTJ504) from Texaco Chemical Company.

The substances according to the invention surprisingly result from their

Structure from free amino and urea groups a much improved Adhesive strength, especially on oxidic surfaces and glass surfaces. The films formed on the surfaces are characterized by high strength, scratch resistance and transparency, high solvent resistance and good miscibility with low molecular weight functional alkoxysilanes, such as 3-aminopropyltrialkoxysilanes, and are very suitable as binders for

Fiberglass finishing.

Another object of the invention is a process for the preparation of the water-soluble, oligomeric or polymeric, ammofunctional urine-alkoxy-silane compounds, which is characterized in that components a), bl) and optionally b2), which have already been described above , in an organic solvent in which the reaction product is soluble, optionally with the addition of catalysts and / or other additives, at temperatures from -20 ° C to 100 ° C, preferably from 0 ° C to 60 ° C, particularly preferably from 0 ° C to 40 ° C, reacting and then cooling.

Catalysts such as e.g. tertiary amines (e.g. triethylamine), tin compounds (e.g. tin-II-octoate, dibutyltin oxide, dibutyltin dilaurate) and other catalysts customary for the reaction of isocyanates, such as those e.g. in Becker / Braun, Kunststoff-Handbuch, Vol. 7, Polyurethane, 1983 Hanser, Munich. Suitable catalysts are also in Adv. Ureth. Be. Techn. 12, 1993, 59-85 and in J. Prakt. Chem., 336, 1994, 185-200.

Preferred solvents are N-methylpyrrolidone, diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, acetone, butyl acetate, methoxypropyl acetate, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, hexanol, octanol, methoxypropanol, methyl diglycol, ethyl diglycol, or butyl diglycol, or butyl diglycol, or methyl diglycol, or butyl diglycol, or methyl diglycol, or butyl diglycol, or methyl diglycol, or methyl diglycol, or methyl diglycol, or methyl diglycol, or methyl diglycol or butyl diglycol Solvent used. Methanol, ethanol, propanol, isopropanol and acetone are particularly preferred. It was surprising for the person skilled in the art to obtain water-soluble, oligomeric or polymeric amino-functional urea-alkoxy-silane compounds, since it is generally known that the reaction of diamines with diisocyanates leads to higher molecular weight oligo- and polyurea compounds, which, however, due to their changed solubility and through crosslinking directly during the reaction from the used

Solvents fail.

Another object of the invention are sizing agents for glass fibers, which are characterized in that they contain, in addition to the usual constituents of a sizing, the water-soluble, oligomeric or polymeric, amino-functional urea-alkoxy-silane compounds as adhesion promoters.

As already described above, the compounds according to the invention can not only be used as adhesion promoters in glass fiber sizes, but can also be applied to glass surfaces for the surface modification of oxidic ones

Solids are used, are used as binders for glass, mineral and wood particles, are used to produce antireflection coatings and are used as paints or paint components.

The invention is illustrated by the following examples.

Examples

The isocyanates used in the experiments were 1,6-diisocyanatohexane (HDI) and isocyanatomethyl-5-isocyanato- 1, 3,3-trimethylycyclohexan (isophorone diisocyanate, IPDI) and Desmodur® N3300, Desmodur ^® N3400 and Desmodur® N3200 from Bayer AG. N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane (AI 120 from OSI-WITCO) and as component b2) D230, EDR 148, ED 600 from Texaco Chemical Company were used as amino component bl).

example 1

Components b1) and optionally b2) were placed in 200 parts of the solvent with cooling. Then component a) was added dropwise and the temperature was kept at 10 to 15 ° C. The mixture was stirred until the solution, e.g. was free of NCO by means of IR spectroscopy.

The "Solubility" column indicates whether the product dissolves during and after the reaction (+) or whether the product fails during or after the reaction (-). Example 2

The "Solubility" column indicates whether the product dissolves during and after the reaction (+) or whether the product fails during or after the reaction (-).

Comparative Example 3

Component bl) was initially introduced into 200 parts of the solvent with cooling. Then component a) was added dropwise and the temperature was kept at 10 to 15 ° C. The mixture was stirred until the solution was NCO-free when tested, for example by means of IR spectroscopy.

* Amine L = N, N-bis (3-aminopropyl) methylamine

The "Solubility" column indicates whether the product dissolves during and after the reaction (+) or whether the product occurs during or after the reaction (-).

Example 4

Components b1) and optionally b2) were placed in 560 parts of the solvent with cooling. Then component a) was added dropwise and the temperature was kept at 10 to 15 ° C. The mixture was stirred until the solution was free of NCO when tested, for example by means of IR spectroscopy.

The "Solubility" column indicates whether the product dissolves during and after the reaction (+) or whether the product fails during or after the reaction (-). The products according to the invention remain in solution during the reaction (corresponds to solubility = + in the tables) and can be applied from the solvents used in the synthesis or, after solvent exchange, from suitable solvents which may contain water. Comparative products which show that not all of the diamino derivatives lead to the products according to the invention are listed in Example 3. These resulted in a clear minus ("-") in solubility (see table).

Example 5

The glass fibers were produced as they are e.g. Incl. Loewenstein, "The Manufacturing Technology of Continuous Class Fibers", Elsevier Scientific Publishing Corp., Amsterdam, London, New York, 1983.

The size consisted of the following components and was applied to glass fiber - with a diameter of 11 μm - using a kiss roll applicator. The glass fibers were then dried at 135 ° C.

Example 6

Use of the coated glass fibers according to the invention

70 parts by weight of polyamide 6 (Durethan® BKV 29, Bayer AG) and 30 parts by weight of glass fibers from Examples 5.1, 5.2 and 5.3 were extruded and granulated on an extruder at an extruder temperature of 250 ° C. . 80 x 10 x 4 mm test bars and tensile bars were produced from the molding compositions on a conventional injection molding machine. Bending strength according to DIN 53 452, tensile strength according to DIN 53 455 and impact strength at room temperature according to Izod (ISO 180 / IC) were tested.

The substances according to the invention applied in sizing agents to glass fibers result in glass fiber reinforced plastics which have tensile and flexural strength and

Impact properties have better properties than corresponding plastics, which are reinforced with common sized glass fibers.

Claims

Patent claims

1. Water-soluble, oligomeric or polymeric, amino-functional urea ff-alk-oxy-silane compounds available by reaction of

a) 1 to 1.8 equivalents of a diisocyanate

b) 2 equivalents of a diamine consisting of

bl) 80 to 100% by weight of a diammoalkoxysilane of the formula (I)

HN(Rl)-Z-N(H)-Y-Si

(OR2) _(3.a) R3 _a (I)

where

Z = C i -Cg-alkylene, C ₅ -C 1 ₀ -cycloalkylene or arylene,

R ¹ = H, C _r C ₆ alkyl or C ₅ -C ₁₀ cycloalkyl,

Y = C ₃ -C ₆ alkylene,

R ² = C _r C ₆ alkyl or C ₅ -C ₁₀ cycloalkyl,

a = 0 to 2 and

R ³ = C _] -C ₆ -alkyl or C ₅ -C _] o-cycloalkyl, and

b2) 0 to 20% by weight of at least one nonionic, hydrophilic compound which contains ether groups, which has two groups reactive towards isocyanate groups, in particular hydroxyl and/or amino groups, per molecule.

. Process for the preparation of compounds according to claim 1, characterized in that the compounds a), b1) and optionally b2) in an organic solvent in which the reaction product is soluble, optionally with the addition of catalysts and/or further additives at temperatures between - 10°C and +100°C, preferably between 0°C and 60°C, are reacted with one another and then cooled.

3. Use of the compounds according to claim 1 for surface modification of oxidic solids, as binders for glass, mineral and wood particles, for promoting adhesion on glass surfaces, as adhesion promoters in sizing agents for sizing glass fibers, for producing anti-reflection layers and as varnishes or varnish components.